Fabrication method for semiconductor device

ABSTRACT

For providing a cleaning technique capable of removing metal contamination at a low temperature and in a short period of time, an aqueous solution containing 0.1 to 15% by weight of hydrochloric acid, 0.01 to 0.3% by weight of hydrofluoric acid and 0.1 to 15% by weight of hydrogen peroxide is used as a cleaning solution upon cleaning a semiconductor substrate after forming a gate electrode of a polymetal structure on the semiconductor substrate.

BACKGROUND OF THE INVENTION

[0001] This invention concerns a fabrication technique for a semiconductor device and, more in particular, it relates to a technique effective to application for a wet cleaning treatment conducted in the fabrication steps for a semiconductor device.

[0002] In the fabrication steps for a semiconductor device, wet cleaning technique proposed by RCA company in USA (so-called RCA cleaning) has been used generally as a method of removing contaminant materials such as obstacles or metals deposited or remained on the surface of silicon substrates.

[0003] The RCA cleaning is a cleaning technique comprising, in combination, (1) a dipping treatment by using a mixed solution of ammonium hydroxide (NH₄OH)+hydrogen peroxide (H₂O₂)+water (referred to as SC-1 solution or APM solution) at 80° C. for about 10 to 20 min, (2) a dipping treatment by using a hydrofluoric acid (HF) at a room temperature, several tens sec and (3) a dipping treatment by using a mixed solution including hydrochloric acid (HCl)+hydrogen peroxide+water (referred to as SC-2 solution or HPM solution) at 80° C. for about 10 min. Among the cleaning solutions described above, the SC-1 solution is used for removing mainly obstacles and the SC-2 solution is used for removing mainly metal contaminant. Further, hydrofluoric acid is used for removing silicon oxide films which become unnecessary in the course of the steps or spontaneous oxide films.

[0004] Metal contamination on the surface of the silicon substrates diffuse by the subsequent heat treatment such as oxidation into gate insulation films or substrates to bring about degradation of device characteristics such as deterioration of insulation withstand voltage for the gate insulation films, fluctuation of gate insulation film/substrate interface energy level and pn-junction destruction. Particularly, LSIs in recent years in which integrated circuits are constituted with refined devices, suffer from degradation of the device characteristics by metals, even with an extremely small amount, on the surface of the silicon substrates. Therefore, in view of the fabrication yield of LSI, it is a predominant factor how to remove metal contamination effectively in the cleaning step.

[0005] The SC-2 solution (mixed solution of hydrochloric acid+hydrogen peroxide+water) used for removing metal contamination in the RCA cleaning described above has no etching function by nature, so that it is difficult to effectively remove metal contamination such as Cu (copper) taken to the surface of the silicon substrates. Accordingly, various improved SC-2 solutions have been proposed with an aim of enhancing the metal removing function of the SC-2 solution. The textbook of Chan & Sze (Chang & Sze, “ULSI Technoloty”, McGRAW-Hill, 1996, p 60-104) and literatures cited therein give detailed explanations on them.

[0006] Japanese Laid-open Patent Application Hei 3(1991)-208899 discloses a technique of removing metal contaminants and fine particle contaminants together by the cleaning of wafers by heating an aqueous solution containing 0.1% or more of hydrochloric acid, 0.05 to 10% of hydrofluoric acid and 0.05 to 10% by weight of hydrogen peroxide at 60° C. to 80° C.

[0007] Japanese Laid-open Patent Application Hei 8(1996)-031781 discloses a technique of removing metal contamination on the wafer surface and contaminants in the surface oxide films by using an aqueous solution containing 0.17% of hydrochloric acid, 0.25% of hydrofluoric acid and 0.1 to 0.2% of hydrogen peroxide.

[0008] Japanese Laid-open Patent Application Hei 8-264499 discloses a technique of removing metals on wafer surface, particularly, Cu (copper) by using an aqueous solution at 60° C. or lower, containing 0.5-3 mol/L of hydrochloric acid, 0.3 to 2.5 mol/L of 0.25% hydrogen peroxide and 0.01 to 0.3% by weight of hydrofluoric acid.

[0009] Japanese Laid-open Patent Application Hei 3(1991)-228327 discloses a technique of removing heavy metal contamination by dipping wafers in an aqueous solution at a normal temperature, containing 3% of hydrochloric acid, 0.4% of hydrofluoric acid and 5% of hydrogen peroxide.

[0010] Japanese Laid-open Patent Application Hei 5(1993)-166777 discloses a technique of removing cross contamination with a less number of steps by using an aqueous solution containing 0.7% of hydrochloric acid, 0.5% of hydrofluoric acid and 0.15% of hydrogen peroxide.

SUMMARY OF THE INVENTION

[0011] The present inventors have made a study on the problems caused in a case of applying the SC-2 solution to cleaning steps for LSI fabricated according to the design rule of 0.18 μm or less.

[0012] As has been described above, for removing metal contamination on the surface of silicon substrates by using the SC-2 solution (hydrochloric acid+hydrogen peroxide+water), since the SC-2 solution has to be kept at a high temperature of about 80° C., there exists a problem that the cleaning apparatus consumes a great amount of electric power. Further, there is also a problem that the composition of the cleaning solution fluctuates greatly because of high temperature treatment to increase the frequency of exchanging the chemical solution. Furthermore, there is also a problem that the space for installing the cleaning apparatus is increased since the heating facility necessary.

[0013] In the recent situation to the wafer-by-wafer treatment along with the increasing size of wafers, short time treatment has been required for the cleaning step with a view point of improving the throughput. However, the SC-2 solution requiring at high temperature and long time treatment hinders wafer by wafer treatment in the cleaning steps.

[0014] The effect of metal contamination has become conspicuous along with refinement of devices, and extremely low metal contamination level is required for deep sub-micron devices. However, since the SC-2 solution used for removing the metal contamination has no etching function, it can not effectively remove metal contamination taken to the substrate surface or the gate insulation film surface. On the other hand, various kinds of improved SC-2 solution in which hydrofluoric acids is added to the SC-2 solution are improved with the etching function for the silicon substrate or the silicon oxide film thereby scraping the silicon substrate or the silicon oxide film to simultaneously remove metals deposited on the surfaces thereof, so that they scrape the silicon substrate or the silicon oxide film excessively to possibly deteriorate the device characteristics.

[0015] Particularly, as a countermeasure for compensating gate delay along with refinement of gate electrodes in deep sub-micron MISFET, metal material such as W (tungsten) is introduced into the gate electrode materials. Therefore, while a cleaning technique capable of efficiently removing metal contamination after the fabrication of the gate electrode has been demanded, when cleaning at high temperature and long time is conducted by using the SC-2 solution containing hydrogen peroxide for ionizing W, the W film constituting the gate electrode is scraped and eliminated. Further, when the improved SC-2 solution containing the hydrofluoric acid described above is used, since hydrofluoric acid etches the gate oxide film at the lower portion of the gate electrode side wall, this may possibly deteriorate the characteristics of the device.

[0016] This invention intend to provide a technique capable of reducing the electric power consumption in a cleaning apparatus.

[0017] Further, this invention intends to provide a technique capable of improving the cleaning performance.

[0018] Further, this invention intends to provide a technique capable of reducing the frequency exchanging for the chemical solution upon cleaning.

[0019] Further, this invention intends to provide a technique capable of decreasing the space for installing a cleaning apparatus.

[0020] Further, this invention intends to provide a technique capable of reducing the cost for the cleaning apparatus.

[0021] Further, this invention intends to provide a technique capable of preventing elimination of a gate electrode upon cleaning after patterning a polymetal gate electrode.

[0022] Further, this invention intends to provide a technique capable of efficiently removing metal contamination with no unnecessary etching of a silicon substrate or a silicon oxide film.

[0023] The foregoing and other objects, as well as novel features of this invention will become apparent by reading the descriptions of the present specification and the accompanying drawings.

[0024] Outlines of typical inventions disclosed in the present application are briefly explained as described below.

[0025] This invention uses, as a cleaning solution for removing metal contamination on the surface of a semiconductor wafer, an aqueous solution containing 0.1 to 15% by weight of hydrochloric acid, 0.01 to 0.3% by weight of hydrofluoric acid and 0.1 to 15% by weight of hydrogen peroxide. The concentration of the hydrochloric acid, hydrofluoric acid and hydrogen peroxide is, preferably, 0.3 to 5% by weight, 0.02 to 0.2% by weight and 0.3 to 5% by weight, respectively, and, further preferably, 0.5 to 3% by weight, 0.03 to 0.1% by weight and 0.5 to 3% by weight, respectively.

[0026] Further, the ratio of hydrochloric acid to hydrofluoric acid contained in the aqueous solution is hydrochloric acid:hydrofluoric acid=5 to 1500:1 (weight ratio), more preferably, hydrochloric acid:hydrofluoric acid=5 to 1000:1 (weight ratio) and, further preferably, hydrochloric acid:hydrofluoric acid=10 to 30:1 (weight ratio).

[0027] Further, outlines of other inventions in the present application are paraphrased and shown briefly.

[0028] 1. A method of fabricating a semiconductor device including the following steps of:

[0029] (a) forming a first film pattern containing a film of a refractory metal base (usually tungsten at high purity, alloy with other metal such as a refractory metal, and those with addition of other additives) on the surface of a silicon base usually impurity doped silicon single crystal region, and other such as silicon germanium alloy, silicon germanium carbon alloy regions) on a first main surface of a wafer,

[0030] (b) acting a first alkaline cleaning solution on the first main surface of the wafer formed with the first film pattern,

[0031] (c) acting a second acidic cleaning solution containing hydrofluoric acid, hydrochloric acid, hydrogen peroxide and water on the first main surface of the wafer formed with the first film pattern and

[0032] (d) applying a high temperature heat treatment at a temperature exceeding 600° C., after completing both of the step (b) and step (c) to the wafer without cleaning by a third cleaning solution containing hydrofluoric acid different in the composition from the second cleaning solution.

[0033] 2. A fabrication method for a semiconductor device according to (1) above wherein the film of the refractory metal base is a film including tungsten or molybdenum as a main constituent ingredient.

[0034] 3. A fabrication method for a semiconductor device according to (2) above wherein the first cleaning solution contains ammonium hydroxide, hydrogen peroxide and water.

BRIEF DESCRIPTION OF THE DRAWINGS

[0035] These and other objects, as well as novel features of this invention will become apparent by reading the descriptions of the present specification and appended drawings, wherein

[0036]FIG. 1 is a cross sectional view for a main portion of a semiconductor device during fabrication steps as a preferred embodiment according to this invention;

[0037]FIG. 2 is a cross sectional view for a main portion during manufacturing steps of the semiconductor succeeding to FIG. 1;

[0038]FIG. 3 is a graph showing the result of an experiment comparing the removal efficiency of copper (Cu) between a case of applying cleaning according to this embodiment and a case of applying cleaning studied by the present inventors in the course of accomplishing this invention;

[0039]FIG. 4 is a graph showing the result of an experiment comparing the removal efficiency of iron (Fe) between a case of applying cleaning according to this embodiment and a case of applying cleaning studied by the present inventors in the course of accomplishing this invention;

[0040]FIG. 5 is a cross sectional view for a main portion during manufacturing steps of the semiconductor succeeding to FIG. 2;

[0041]FIG. 6 is a cross sectional view for a main portion during manufacturing steps of the semiconductor succeeding to FIG. 5;

[0042]FIG. 7 is a cross sectional view for a main portion during manufacturing steps of the semiconductor succeeding to FIG. 6;

[0043]FIG. 8 is an explanatory view illustrating an example of a cleaning apparatus used in the fabrication step for a semiconductor device as an embodiment according to this invention;

[0044]FIG. 9 is an explanatory view illustrating another example of a cleaning apparatus used in the fabrication step for a semiconductor device as an embodiment according to this invention;

[0045]FIG. 10 is an explanatory view illustrating a cleaning section of the cleaning apparatus showing in FIG. 8 and FIG. 9;

[0046]FIG. 11 is a cross sectional view for a main portion of a semiconductor device during fabrication steps as another preferred embodiment according to this invention;

[0047]FIG. 12 is a schematic view illustrating a cleaning apparatus used in fabrication steps for a semiconductor device as another preferred embodiment according to this invention;

[0048]FIG. 13 is an explanatory view illustrating a cleaning section of the cleaning apparatus showing in FIG. 12;

[0049]FIG. 14 is a cross sectional view for a main portion during manufacturing steps of the semiconductor succeeding to FIG. 11;

[0050]FIG. 15 is a cross sectional view for a main portion during manufacturing steps of the semiconductor succeeding to FIG. 14;

[0051]FIG. 16 is a cross sectional view for a main portion during manufacturing steps of the semiconductor succeeding to FIG. 15;

[0052]FIG. 17 is a graph illustrating a relation between a cleaning time and a metal contamination removal efficiency in an experiment using the cleaning solution of this invention; and

[0053]FIG. 18 is a graph illustrating the result of an experiment for measuring the effect of the ratio of hydrochloric acid to hydrofluoric acid contained in the cleaning solution according to this invention on an etching rate of a silicon oxide film.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT

[0054] Before explaining preferred embodiments of this invention, fundamental meanings of terms used in the present specification are to be described below.

[0055] “Semiconductor device” in this specification means not only those prepared on single crystal silicon substrates but also includes those prepared on other substrates such as SOI (Silicon On Insulator) substrate or substrates for fabrication of TFT (Thin Film Transistor) liquid crystal, unless otherwise specified.

[0056] Further, “semiconductor wafer (semiconductor substrate)” means silicon and like other semiconductor single crystal substrates (generally in substantially planer circular shape), sapphire substrates, glass substrates, as well as other insulative or semi-insulative or semiconductor substrates and composite substrates thereof used for the fabrication of a semiconductor device.

[0057] Further, expression “including A” used for materials (solid, solution, gas) generally mean not only pure materials but also those compounds, mixed crystals, mixtures, composites bodies, as well as those containing other additives and impurities, within a range that the fundamental properties do not change greatly. For example, it will be apparent that “silicon wafer” includes wafers entirely consisting of silicon single crystals but also generally includes those containing other materials region in the inside or on the surface, for example, an Si_(x)Ge_(Y) channel region and SOI substrates as described above.

[0058] For the preferred embodiments to follow, they are conveniently explained, optionally being divided into plural sections or embodiments but, unless otherwise specified, they are not independent of each other but in such a relation that one constitutes, partially or wholly, modified embodiments, details, supplemental explanations of the other.

[0059] Further, when the numbers of constituents (including number, numerical value, amount, range and the like) are referred to in the following embodiments, they are not restricted to particular numbers but may be more than or less than the particular numbers unless otherwise specified, or except for the case where they are apparently restricted to the particular numbers.

[0060] Furthermore, in the following embodiments, the constituent factors (also including constituent steps) are not always essential unless otherwise specified or considered apparently essential in view of principle. In the same manner, when the shape and the positional relation for the constituent factors are referred to in the following embodiments, they also include those substantially closer to or similar with the shape and the like unless otherwise specified, or except for the case where they are apparently considered to be excluded in view of principle. This is also applicable to the numeral value and the range described above.

[0061] Further, throughout the drawings for explaining the embodiments, those having identical functions carry the same reference numerals, for which duplicate explanations will be omitted.

[0062] Further, in this embodiment, MOS•FET (Metal Oxide Semiconductor Field Effect Transistor) exemplifying a field effect transistor is simply referred to as MOS, a p-channel type MOS•FET is simply referred to as pMOS and a n-channel MOS•FET is simply referred to as nMOS. While MOS•FET includes MIS•FET (Metal Insulator Semiconductor Field Effect Transistor) but they are explained by MOS•FET as a representative.

[0063] Further, treatment such as plurality kinds of cleaning is explained such that they are practiced in a plurality of places, chambers or tanks optionally but this does not exclude plural kinds of treatment conducted in one identical place or the like. The description for the embodiment also include a case of using the treatment section in common.

[0064] In the subsequent embodiments, the wafer cleaning temperature means not a temperature for the cleaning solution but a wafer temperature during cleaning. Further, the unit indicating the ingredients for the cleaning solution (wt % or the like) represents the actual amount of the ingredients as the object.

[0065] (Embodiment 1)

[0066] The embodiments of this invention are to be explained in details with reference to the drawings.

[0067] In this embodiments, this invention is explained with reference to FIG. 1 to FIG. 7, for example, to a case of application to a fabrication method for a semiconductor device having a CMOS (Complementary MOS) circuit. A fabrication method of this embodiment to be explained later is described in Japanese Patent Application No. 2000-127269 (filed on Apr. 27, 2000) filed by the present inventor.

[0068]FIG. 1 is a cross sectional view for a main portion of a semiconductor device during fabrication step. At first, after forming a device isolation trench 2 of about 350 nm depth to a semiconductor substrate including p-type single crystal silicon having a specific resistivity, for example, of about 1 to 10 Ωcm (hereinafter referred to as a substrate) 1 by using photolithography and dry etching, a silicon oxide film 3 is deposited on the substrate 1 including the inside of the trench by means of a CVD method. Successively, the surface of the silicon oxide film 3 above the trench is planarized by chemical mechanical polishing (CMP). Thus, a groove-shaped device isolation portion 2A (trench isolation) is formed. Then, boron is ion implanted to an nMOS forming region of the substrate 1 and phosphorus is ion implanted to a pMOS forming region of the substrate 1, to form a p-well 4 in the nMOS forming region and an n-well 5 in the pMOS forming region.

[0069] Then, the substrate 1 is steam-oxidized to form a gate insulation film 6, for example, of about 6 nm thickness on the p-well 4 and the n-well 5. The thickness of the gate insulation film 6 herein means a thickness converted to that of silicon dioxide, which does not sometimes agree with an actual film thickness.

[0070] The gate insulation film 6 may be constituted with a silicon oxynitride film instead of the silicon oxide film. Since the silicon oxynitride film has a higher effect of suppressing occurrence of the interface energy level or reducing electron traps in the film compared with the silicon oxide film, it is possible to improve the hot carrier resistance and improve the insulation withstand of the gate insulation film 6. The silicon oxynitride film can be formed, for example, by applying a heat treatment to the substrate 1 in a nitrogen gas-containing atmosphere such as NO, NO₂ or NH₃. Further, the same effect as above can be obtained also by forming a gate insulation film 6 including silicon oxide to each of the surfaces of the p-well 4 and the n-well 5 and then applying a heat treatment to the substrate 1 in the nitrogen-containing gas atmosphere described above to segregate nitrogen to the interface between the gate insulation film 6 and the substrate 1.

[0071] Further, the gate insulation film 6 may be formed also, for example, with a composite insulation film of a silicon nitride film or a silicon oxide film and a silicon nitride film. If the thickness of the gate insulation film 6 including silicon oxide is reduced to less than 5 nm and, particularly, less than 3 nm as converted to the thickness of silicon dioxide, lowering of the insulation withstand voltage caused by the occurrence of direct tunnel current or hot carriers due to stresses becomes conspicuous. Since the silicon nitride film has a higher dielectric constant than the silicon oxide film, the thickness thereof converted as that of the silicon dioxide is decreased compared with an actual film thickness. That is, in a case having the silicon nitride film, even if it is physically thick, a capacitance equal with that of a relatively thin silicon dioxide film can be obtained. Accordingly, when the gate insulation film 6 is constituted with a single silicon nitride film or a composite film thereof with a silicon oxide film, since the effective film thickness can be increased more than that of the gate insulation film constituted with the silicon oxide film, reduction of the insulation withstand voltage caused by occurrence of the tunnel leakage current or the hot carriers can be improved. Further, since impurities less penetrate through the silicon oxynitride film compared with the silicon oxide film, when the gate insulation film 6 is constituted with the silicon oxynitride film, fluctuation of the threshold voltage caused by diffusion of impurities in the gate electrode material to the semiconductor substrate can be suppressed.

[0072] The film thickness of the single insulation film or a composite insulation film converted to that silicon dioxide (hereinafter also simply referred to as converted film thickness) dr is a film thickness defined by the following equation: ${dr} = {\sum{\frac{ɛ\quad i}{ɛ\quad s}{di}}}$

[0073] where εi is a specific dielectric constant of the insulation film as an object, di represents a film thickness and εs represents a specific dielectric constant of silicon dioxide:

[0074] For instance, the dielectric constant for silicon oxide (SiO₂) and silicon nitride (Si₃N₄) are, respectively, 4 to 4.2 and 8. Then, the thickness of the silicon nitride film, for example, of 6 nm thickness is calculated as 3 nm assuming the dielectric constant of silicon nitride is twice as the dielectric constant of silicon oxide. That is, the capacitance is equal between the gate insulation film including the silicon nitride film of 6 nm thickness and the gate insulation film including the silicon oxide film of 3 nm thickness. Further, the capacitance of the gate insulation film of a composite film including a silicon oxide film of 2 nm thickness and a silicon nitride film of 2 nm thickness (converted thickness equal 1 nm) is equal with the capacitance of a gate insulation film including a single silicon oxide film of 3 nm thickness.

[0075] Then, as shown in FIG. 2, a gate electrode 7 and a cap film 8 thereon are formed by usual photolithographic technique and dry etching over the gate insulation film 6. That is, after depositing, a low resistance polycrystal silicon film, a tungsten nitride (WN) film, a tungsten (W) film and the silicon nitride film successively from the lower layer over the substrate 1, for instance, a photoresist pattern is formed thereover so as to cover the gate electrode forming region while exposing other areas. Successively, using the photoresist pattern as an etching mask, the silicon nitride film, the tungsten film, the tungsten nitride film and the low resistance polycrystal silicon film exposed therefrom are removed, to form a gate electrode 7 of a so-called polymetal gate structure including a cap film 8 including a silicon nitride film, a low resistance polycrystal silicon film, a tungsten nitride film and a tungsten film. The low resistance polycrystal silicon film can be formed by a CVD method, and the tungsten nitride film and the tungsten film can be formed by a sputtering method. A titanium nitride (TiN) film may also be used instead of the tungsten nitride film. Further, a molybdenum (Mo) film may also be used instead of the tungsten film. Further, the gate electrode 7 may be formed of a lamination film prepared by depositing a tungsten silicide film, titanium silicide film or cobalt (Co) silicide film on the low resistance single crystal silicon film. Further, as the material for the gate electrode 7, an alloy of polycrystal or single crystal silicon (Si) or germanium (Ge) may also be used.

[0076] Then, in this embodiment, the following wafer-by-wafer cleaning treatment is applied, for example, to the substrate 1.

[0077] At first, a first wafer-by-wafer cleaning is a cleaning treatment mainly for removing fine particles (organic material) deposited to the substrate 1. The fine particles are, for example, dusts formed from semiconductor fabrication apparatus, jigs or human bodies or reaction products formed upon etching or film deposition treatment, and various materials are deposited in various forms on the substrate. In this case, substrates 1 are cleaned wafer-by-wafer by using a mixed solution of ammonium hydroxide (NH₄OH), hydrogen peroxide (H₂O₂) and water (H₂O).

[0078] Succeeding second wafer-by-wafer cleaning is a cleaning treatment mainly for removing metals deposited on the substrate. The metals are deposited from the semiconductor fabrication apparatus, atmospheric air, human bodies, solution chemicals or predetermined materials onto the substrate 1 and the mode of contamination can include, finely particulate shape deposition, ionically adsorption or implantation into the substrate 1 during plasma process. In this embodiment, upon the second cleaning, a cleaning solution prepared by blending an etching solution having a performance capable of etching silicon, oxide film or both of them, a pH controller and an oxidizer was used. Specifically, the cleaning treatment includes, for example, the followings. The cleaning solution used comprises, for example, hydrofluoric acid (HF:etching solution described above) hydrochloric acid (HCl:pH controller): hydrogen peroxide (H₂O₂:oxidizer): water (H₂O)=0.4:10:10:500. The treating temperature is conducted, for example, at a room temperature (about 23° C.). Further, treating time is about 5 min at the longest. In this embodiment, it may be preferably about 1 min, specifically about 40 to 50 sec.

[0079] In the second wafer-by-wafer cleaning, in this embodiment, metals in the surface layer of the substrate 1 (silicon) can also be removed by conducting oxidation to the surface of the substrate 1 (silicon) by hydrogen peroxide and etching of the oxide film (silicon oxide film) by hydrofluoric acid to an extent of a monolayer simultaneously in one identical step. That is, since the cleaning power can be improved, it is possible to enhance the yield, the reliability and the performance of the semiconductor device.

[0080] Then, FIG. 3 and FIG. 4 shows the result of an experiment comparing the removal efficiency of copper (Cu) and iron (Fe) between a case of applying cleaning in this embodiment and applying cleaning studied by the present inventors for accomplishing the invention. FIG. 3 shows a copper removal efficiency and FIG. 4 shows an iron removal efficiency. In each of the graphs, the left part illustrates this embodiment and the right part illustrates the cleaning technique studied by the present inventors. As seen from FIG. 3, when cleaning in this embodiment is used, while the copper removal efficiency is somewhat lower compared with that of the cleaning studied by the present inventors, but a sufficient cleaning result can be obtained. Further, if can be seen from FIG. 1 that the iron removal efficiency is remarkably improved in the cleaning of this embodiment than in the cleaning studied by the present inventors.

[0081] Further, in the cleaning treatment of this embodiment, since the metal contamination of the substrate 1 can be removed rapidly, the treating time for wafer-by-wafer cleaning can be shortened. Accordingly, even when the wafer-by-wafer cleaning is employed, the development and production time for a semiconductor device can be shortened to improve the throughput in the fabrication steps for the semiconductor device.

[0082] Further, in the cleaning treatment of this embodiment, the temperature for the cleaning can be lowered by the effect of fluorine, and cleaning can be conducted at a room temperature or a further lower treating temperature. Accordingly, it is possible to reduce the electric power consumption of the cleaning apparatus. Further, the frequency for changing the chemical solutions during cleaning can be decreased. Further, since the heating facility is no more required, the space for installing cleaning apparatus can be reduced. Further, since the heat facility is no more required, cost for the cleaning apparatus can be decreased. Accordingly, the fabrication cost for the semiconductor device can be decreased. Further, since the cleaning can be conducted at a lower temperature and in a short period of time, the oxidizing rate of tungsten constituting the gate electrode 7 can be retarded. That is, oxidation for a portion of the gate electrode 7 during cleaning can be reduced. Accordingly, it is possible to improve the yield, reliability and performance of the semiconductor device can be improved.

[0083] Further, in the cleaning treatment according to this embodiment, since the cleaning temperature can be lowered, the reaction rate between the oxidizer and the polymetal gate electrode (tungsten film or tungsten nitride film) can be lowered irrespective of the use of the oxidizer. Therefore, elimination of the gate electrode 7 by cleaning can be prevented. Accordingly, it is possible to improve the yield, reliability and performance of the semiconductor device having the polymetal gate electrode structure.

[0084] Further, in the cleaning treatment according to this embodiment, since the pH controller (strong acid) is contained in the cleaning solution, hydrogen ions are adsorbed on the surface of the substrate during cleaning which can promote positive charging on the surface of the substrate 1 (silicon) so that re-deposition of positively charged metal ions such as of copper, gold, aluminum, iron or nickel (for example, adsorption of copper on silicon to form silicide) can be suppressed or prevented. Accordingly, it is possible to improve the yield, reliability and performance of the semiconductor device.

[0085] For the etching solution, ammonium fluoride (NH₄F) or tetramethyl ammonium fluoride (TMAF) may also be used instead of hydrofluoric acid. Use of hydrofluoric acid can provide the effect of facilitating the use since the constitution is simple and a lot of date of experience are available to be used in the fabrication steps for semiconductor device. However, in the use of hydrofluoric acid, since the etching rate for silicon dioxide films is high and excess etching is caused, the amount of hydrofluoric acid has to be decreased. Accordingly, preparation of the cleaning solution (chemical solution) is sometimes difficult when hydrofluoric acid is used. On the other hand, in the use of ammonium fluoride or trimethyl ammonium fluoride, the amount of HF₂ ⁻ can be decreased even when the chemical is supplied in an amount identical with that of hydrofluoric acid. Accordingly, when ammonium fluoride or trimethyl ammonium fluoride is used, it can be supplied in a greater amount than that of hydrofluoric acid, so that preparation of the cleaning solution (chemical solution) can be facilitated. Further, for the pH controller, sulfuric acid (H₂SO₄) or nitric acid (HNO₃) may also be used instead of hydrochloric acid.

[0086] After the second cleaning as described above, water washing is applied using, for example, pure water, super pure water on every sheet of substrates. Successively, drying is applied for each substrate sheet. In the drying, spin drying is applied, for example, in an inert gas atmosphere such as a nitrogen or argon gas. That is, drying is applied in a low-oxygen atmosphere while rotating the substrate 1 in a direction parallel with a main plane thereof. This can suppress or prevent formation of water marks on the surface of the substrate 1. The drying method can be modified variously and, for example, a method of steam drying in an isopropanol atmosphere, a hot blow drying or IR-ray drying method may also be used.

[0087] After the wafer-by-wafer cleaning as described above, as shown in FIG. 2, an n⁻-semiconductor region 11 at low impurity concentration is formed in the p-well 4 by ion implanting, for example, phosphorus or arsenic and a p⁻-semiconductor region 12 at low impurity concentration is formed in the n-well 5 by ion implanting, for example, boron to the substrate 1 while using the gate electrode 7 as a mask. Successively, as shown in FIG. 5, an insulation film, for example, comprising a silicon nitride film is deposited by a CVD method and etched anisotropically to form a side wall spacer 13 on the side wall of the gate electrode 7. Subsequently, an n⁺-semiconductor region 14 (source and drain) at high impurity concentration is formed in the p-well 4 by ion implanting phosphorus or arsenic and a p-type semiconductor region 15 (source and drain) is formed to the n-type well by ion implanting boron or the like.

[0088] Then, a silicide layer 9 is formed on the surface of the n-type semiconductor region 14 (source and drain) and the surface of the p⁺-type semiconductor region 15 (source and drain) by depositing a metal film, for example, of titanium or cobalt by a sputtering method and then removing the unreacted metal film after the heat treatment. nMMOSQn and pMOSQp are completed up to this step.

[0089] Then, as shown in FIG. 6, an insulation film 18 comprising a silicon oxide film or the like is deposited on the substrate 1 by a CVD method and, successively, the insulation film 18 is dry etched by using a photoresist film as a mask to form a contact hole 20 above the n⁺-type semiconductor region 14 (source and drain) and a contact hole 21 above the p⁺-type semiconductor region 15 (source and drain). Further, a contact hole 22 is formed also above the gate electrode 7. The insulation film 18 is constituted with a highly reflowing film capable of burying a narrow space of the gate electrodes 7, 7, for example, a BPSG (Boron-doped Phospho Silicate Glass) film. Further, it may be constituted with an SOG (Spin On Glass) film formed by a spin coating method.

[0090] Then, a plug 23 is formed to the inside of each of the contact holes 20, 21 and 22. The plug 23 is formed, for example, by depositing a titanium nitride film, a tungsten film and the like by a CVD method on the upper portion of the insulation film 18 including the insides of the contact holes 20, 21 and 22 and then removing the unnecessary titanium nitride film and the tungsten film in the upper portion of the insulation film 18 by a chemical mechanical polishing (CMP) method or an etching back method to leave the films only in the inside of the contact holes 20, 21 and 22.

[0091] Then, as shown in FIG. 7, first layer wirings 24 to 30 including tungsten or the like are formed over the insulation film 18. The first layer wirings 24 to 30 are formed, for example, by depositing a tungsten film over the insulation film 18 by a sputtering method and then dry etching the tungsten film using a photoresist film as a mask. The first layer wirings 24 to 30 are electrically connected through the contact holes 20, 21 and 22 with the source and drain (n⁺-semiconductor region) of nMOSQn and source and drain (p⁺-semiconductor region ) of pMOSQp, or the gate electrode 7. Subsequently, a semiconductor device is fabricated in accordance with an ordinary process for a semiconductor device having a CMOS circuit.

[0092] Then, FIG. 8 to FIG. 10 show an example of cleaning apparatus used in the wafer-by-wafer cleaning. The constitution of the cleaning apparatus is not restricted only to the following but may be modified variously.

[0093] A cleaning apparatus 35A shown in FIG. 8 illustrates an example of a serial type cleaning apparatus. First to third cleaning sections 38 to 40 are disposed between a loader 36 and an unloader 37. Further, each of transportation arms 41 a-41 d is disposed between each of the sections. Wafer cassettes 42 a are accommodated in the loader 36. The wafer cassette 42 a accommodates a plurality of substrates 1 (semiconductor wafers). The substrates 1 contained in the wafer cassette 42 a in the loader 36 are taken out wafer-by-wafer by the transportation arm 41 a and then transported to the first cleaning section 37.

[0094] In the first cleaning section 37, the first wafer-by-wafer cleaning described above is applied. The substrates 1 after completion of the first wafer-by-wafer cleaning are taken out by the transportation arm 41 b and transported to the second cleaning section 38 at the subsequent stage. In the second cleaning section 38, the second wafer-by-wafer cleaning is applied. That is, this is a cleaning treatment using the cleaning solution of this embodiment as described above. The substrates 1 after completion of the second wafer-by-wafer cleaning are taken out by the transportation arm 41 c and transported to the third cleaning section 39 at the succeeding stage. In this stage, cleaning, for example, by hydrofluoric acid is possible. Each of the first to third cleaning section 37 to 39 has a structure capable of spin drying as described above. The substrates 1 after completion of the third wafer-by-wafer cleaning are taken out by the transportation arm 41 d and accommodated in the cassette 42 b in the unloader 37.

[0095] A cleaning apparatus 35B shown in FIG. 9 illustrates an example of a multi-chamber type cleaning apparatus. A plurality of wafer cassettes 42 a to 42 d are accommodated in a substrate entry/delivery section 43. Each of the wafer cassettes 42 a to 42 d can accommodate a plurality of substrates 1. About at the center of the cleaning apparatus 35B, a transportation channel 44 is located, and first to third cleaning sections 37 to 39 and sections 45 a to 45 c are located on both right and left sides (upper and lower sides in the drawing) thereof. The sections 45 a to 45 c are, for example, film forming section such as for forming the gate insulation film or forming the interlayer insulation film and etching sections for patterning the conductor films or holes.

[0096] The substrate 1 accommodated in any of the wafer cassettes 42 a to 42 d are mounted on a transportation body 44 a of the transportation channel 44 by a transportation arm or the like and then transported in a state being mounted on the transport body 44 a along the transportation channel 44 to the first to third cleaning sections 37 to 39 or sections 45 a to 45 c. The substrates 1 after completion of the predetermined treatment are transported along the transportation channel 44 in the same manner as described above and transported to the succeeding first to third cleaning sections 37 to 39 or sections 45 a to 45 c. The transportation channel may be of a structure having a non-oxidative atmosphere such as a nitrogen gas or argon gas. The substrates 1 after completion of the entire treatment are again carried along the transportation channel 44 to the substrate entry/delivery section 43 and then accommodated in predetermined wafer cassette 42 a to 42 d by way of the transportation arm or the like. Since the cleaning apparatus 35B can conduct parallel treatment and conduct cleaning treatment just after a predetermined treatment, the fabrication efficiency of the semiconductor device can be improved remarkably. Further, since the cleaning can be applied just after the predetermined treatment, deposition of obstacles can be reduced to improve the yield and the reliability of the semiconductor device.

[0097]FIG. 10 shows an example of a second cleaning section 38 for the cleaning apparatus 35A or 35B. A substrate 1 is mounted on supports 46. A stopper 46 a is disposed at the top end of each support 46, by which the substrate 1 is supported. The support 46 is pivotally supported by a shaft 47 such that it can rotate horizontally relative to the surface of the substrate 1 to be cleaned. Nozzles 48 a and 48 b are disposed above the substrate 1. The nozzle 48 a is for supplying, for example, the cleaning solution of this embodiment to the surface of the substrate 1 to be cleaned. Further, the other nozzle 48 b is for supplying pure water or super pure water to the surface of the substrate 1 to be cleaned. In the cleaning treatment, after mounting a sheet of substrate 1 on the supports 46 a and then supplying a cleaning solution from the nozzle 48 a to the surface of the substrate 1 to be cleaned, cleaning treatment is applied while rotating the supports 46 horizontal to the surface of the substrate 1 to be cleaned. The water washing is conducted in the same manner. Further, the structure in the first cleaning apparatus 37 is substantially identical.

[0098] (Embodiment 2)

[0099] The fabrication method in this embodiment is to be explained with reference to FIG. 11 to FIG. 18. At first, as shown in FIG. 11, after forming a device isolation trench 2 on the main surface of a substrate 1 (since the substrate is transported to each of the steps and treated in the form of a wafer, it is sometimes referred to also as a wafer) including p-type single crystal silicon, a p-well 4 is formed to a portion of the substrate 1 and an n-well 5 is formed to other portion. The steps so far are identical with the Embodiment 1 described above.

[0100] Then the surface of the substrate 1 is cleaned. This cleaning is conducted for forming a clean gate insulation film on the surface of the p-well 4 and on the surface of the n-well 5. FIG. 12 is a schematic view illustrating a serial type wafer-by-wafer cleaning apparatus 100 used in the cleaning step. First to third cleaning sections 103, 104 and 105, and a drying section 106 are disposed in this order between a loader 101 and an unloader 102 of the wafer-by-wafer cleaning apparatus 100. Further, each of transportation arms 108 a to 108 e for transporting the wafers (substrates) 1 are disposed between each of the sections (103 to 106). A plurality of wafers 1 each formed with the p-well 4 and the n-well 5 are entered being accommodated in a wafer cassette 109 a to the loader 101. The wafers 1 are taken out one by one by the transportation arm 108 a from the wafer cassette 109 a and then transported to first to the first cleaning section 103.

[0101] In the first cleaning section 103, the surface of the wafer 1 is cleaned to remove obstacles by using a well-known SC-1 solution (APM solution) including a mixed solution of ammonium hydroxide (NH₄OH), hydrogen peroxide (H₂O₂) and water (H₂O).

[0102]FIG. 13 is a schematic view illustrating the inner structure of a cleaning section 103. A wafer 1 is placed, with the main surface thereof facing up, over four supports 111 each disposed to the upper end of a shaft 110 rotating in a horizontal plane and held and secured by stoppers 112 disposed to the supports 111.

[0103] In the cleaning section 103, the SC-1 solution and 33 pure water are supplied to the surface of the wafer 1 by a spraying method. That is, two nozzles 113 a and 113 b are disposed above the wafer 1 placed on the supports 111 and the SC-1 solution is supplied from one of them (nozzle 113 a) to the surface of the rotating wafer 1. The cleaning is applied while setting the temperature of the wafer 1 to about 80° C. and for a treating time of about 10 to 20 min. In the cleaning treatment by the spraying method, different from the method of dipping wafer 1 in the cleaning solution, since the temperature of the cleaning solution discharged from the nozzle 113 a is lowered till the solution reaches the surface of the wafer 1, the cleaning solution has to be heated to a temperature higher than 80° C. in order to keep the temperature of the wafer 1 at 80° C. during cleaning.

[0104] When the cleaning with the SC-1 solution is completed, pure water is supplied from the other nozzle 113 b to the surface of the rotating wafer 1 and rinsing is applied for removing the SC-1 solution. Further, the inner structure for the second cleaning section 104 and the third cleaning section 105 is constituted substantially identical with that of the first cleaning section 103.

[0105] Then, the wafer 1 is transported by the transportation arm 108 b from the first cleaning section 103 to the second cleaning section 104. A new wafer 1 is transported from the wafer cassette 109 a to the first cleaning section 103 by way of the transportation arm 108 a and cleaning with the SC-1 solution described above is applied.

[0106] The wafer transported to the second cleaning section 104 is subjected to cleaning at a room temperature for several tens second by using well-known hydrofluoric acid (HF:water=1:99). As shown in FIG. 14, the silicon oxide film 4 on the surface of the wafer 1 is wet-etched by conducting the cleaning treatment and the surface of the p-well 4 and the surface of the n-well 5 are exposed.

[0107] Then, the wafer 1, after subjected to rinsing treatment with pure water, is transported from the second cleaning section 104 to the third cleaning section 105 by a transportation arm 108 c. In the third cleaning section 105, a cleaning treatment is conducted for removing metals such as Cu deposited on the surface of the p-well 4 and the surface of the n-well 5 exposed by the hydrofluoric acid cleaning.

[0108] The cleaning solution used in this embodiment is an aqueous solution containing 0.1 to 15% by weight of hydrochloric acid, 0.01 at 0.3% by weight of hydrofluoric acid and 0.1 to 15% by weight of hydrogen peroxide. The concentration of hydrochloric acid, hydrofluoric acid and hydrogen peroxide are, preferably, 0.3 to 5% by weight, 0.02 to 0.2% by weight and 0.3 to 5% by weight, preferably, and, more preferably, 0.5 to 3% by weight, 0.03 to 0.1% by weight and 0.5 to 3% by weight, respectively. If the concentration of hydrofluoric acid is less than the lower limit of the range described above (0.01% by weight), no removal effect for metal contamination can be obtained. On the other hand, if the upper limit of the concentration of hydrofluoric acid exceeds the upper limit of the above range (0.3% by weight), the etching amount of the substrate 1 is increased to result in problems such as lowering of the surface flatness. Accordingly, it is important to lower the concentration of the added hydrofluoric acid.

[0109] The cleaning solution in this embodiment has a composition in which a slight amount of hydrofluoric acid is added to the well-known SC-2 solution (HPM solution) used with an aim of removing metal contamination. Since the cleaning solution contains highly electron attractive F (fluorine), metals are easily dissolved in the cleaning solution and hydrofluoric acid added in a slight amount slightly etches the surface of the substrate 1, so that it has a feature capable of removing metals taken to the surface of the substrate 1 at a low temperature and in a short period of time. Further, since hydrogen ions derived from hydrochloric acid are adsorbed to the surface of the wafer 1 to promote positive (+) charging, re-deposition of metal ions detached from the surface of the wafer 1 can also be suppressed.

[0110] The cleaning solution in this embodiment can be used within a range of temperature about from 15° C. to 40° C. with no requirement for elevating the temperature upon use and an appropriate temperature range is usually about from 16° C. to 35° C. and, preferably, about 18° C. to 28° C. The treating time is within the temperature range is about 5 min at the longest and usually a range from 50 sec to 2 min may suffice.

[0111] Since metal contamination on the surface of the wafer 1 can be removed efficiently by using the cleaning solution in this embodiment, the quality of the gate insulation film formed after the cleaning step can be improved.

[0112] Further, since it is not necessary to elevate the temperature of the cleaning solution in this embodiment upon use, it can provide effects such that (1) the electric power consumption of the wafer-by-wafer cleaning apparatus 100 can be reduced, (2) the size of the wafer-by-wafer cleaning apparatus 100 can be decreased by so much as the heating facility is not necessary, and (3) the exchanging frequency of the cleaning solution is decreased since the composition thereof less fluctuates, to reduce the operation cost of the wafer-by-wafer cleaning apparatus 100. Further, since the cleaning time can be shortened remarkably compared with the case of using the SC-2 solution, it is possible to improve the throughput of the cleaning step and formed the wafer-by-wafer treatment.

[0113] Then, after rinsing with pure water, the wafer 1 is transported from the third cleaning section 105 to the drying section 105 by the transportation arm 108 d. In the drying section 106, water content on the surface is removed by rotating the wafer 1 at a high speed. An inert gas such as a nitrogen or Ar (argon) gas is filled in the inside of the drying section 106 to prevent formation of water marks on the surface of the wafer 1. As the method for the drying treatment, a method of steam drying in an isopropanel atmosphere or a method of drying using hot blow or IR-rays may also be used in addition to the spin drying method described above.

[0114] The wafer 1 after completion of the drying is taken out by the transportation arm 108 e from the drying section 106, accommodated in the wafer cassette 109 b in the unloader 102 and then transported to the next step. As described above, wafers are applied with the cleaning treatment wafer-by-wafer and obstacles or metal contaminations on the surface are removed.

[0115] Then, as shown in FIG. 15, a substrate 1 is thermally oxidized to form a gate insulation film 6 including a silicon oxide film of about 6 nm thickness on the surface of the p-well 4 and the surface of the n-well 5. The gate insulation film 6 may be constituted with a silicon oxynitride film instead of the silicon oxide film. Further, it may be constituted with an insulation film such as a silicon nitride film, a composite insulation film of a silicon oxide film and a silicon nitride film or a tantalum oxide film which has higher dielectric constant than the silicon oxide film.

[0116] Then, as shown in FIG. 16, a gate electrode 7 having a gate length of about 0.13 μm to 0.14 μm is formed above the gate insulation film 6. The gate insulation film 7 is formed by depositing a polycrystal silicon film of about 100 nm thickness doped with an n-impurity such as phosphorus (P) over the gate insulation film 6 by a CVD method, successively, depositing a WN (tungsten nitride) film of about 5 nm thickness and a W film of about 50 nm thickness by a sputtering method thereover and, further, depositing a silicon nitride film 9 of about 100 nm thickness further thereover by the CVD method and then patterning the films by dry etching using a photoresist film as a mask. Further, gate electrode 7 may also be constituted with a laminate film of a polycrystal silicon film, a WN film and Mo film by using an Mo (molybdenum) film instead of the W film.

[0117] Metal such as W as a portion of the gate electrode material is deposited on the surface of the substrate 1 formed with the gate electrode 7. The metal deposited on the surface of the substrate 1 diffuses into the gate insulation film 6 or into the substrate 1 by a subsequent heat treatment such as oxidation to bring about degradation of device characteristics such as deterioration of insulation withstand voltage of the gate insulation film 6, fluctuation of gate insulation film/substrate interface energy level and pn-junction destruction. In view of the above, after removing the photoresist film used as the pattern for the gate electrode 7 by an ashing treatment, a cleaning treatment is applied for removing metals or obstacles remained on the surface of the silicon substrate 1.

[0118] In this cleaning step, it is required to reliably remove metal contamination while suppressing etching (scraping) of the gate insulation film 6 or the substrate 1 as less as possible. Particularly, in a process of forming the gate electrode 7 having a fine gate length of about 0.13 μm to 0.14 μm as in this embodiment, when the gate insulation film 6 below the side wall of the gate electrode 7 is isotropically etched to form under cuts, deterioration of characteristics such as lowering of the withstand voltage of the gate insulation film 6 tends to be caused. Accordingly, it is not preferred to use a cleaning solution containing hydrofluoric acid at a high concentration in this cleaning step.

[0119] Further, in a case where the gate electrode 7 comprises a polymetal structure as in this embodiment, it is required to surely remove metal contamination without dissolving or eliminating metals constituting the gate electrode 7. Accordingly, it is not preferred to use the SC-2 solution for conducting a treatment at high temperature for long time such as 80° C. and 10 min in this cleaning step.

[0120] Therefore, in this cleaning step, a cleaning solution of this invention including an aqueous solution containing 0.1 to 15% by weight of hydrochloric acid, 0.01 to 0.3% by weight of hydrofluoric acid and 0.1 to 15% by weight of hydrogen peroxide used in the step of forming the gate insulation film 6 is used. Also in this case, the concentration of the hydrochloric acid, hydrofluoric acid and hydrogen peroxide are 0.3 to 5% by weight, 0.02 to 0.2% by weight and 0.3 to 5% by weight, respectively, and, more preferably, 0.5 to 3% by weight, 0.03 to 0.1% by weight and 0.5 to 3% by weight, respectively.

[0121] Specifically, the cleaning apparatus 35A shown in FIG. 8, the cleaning apparatus 35B shown in FIG. 9 or the wafer-by-wafer cleaning apparatus 100 shown in FIG. 12 is used and obstacles at the surface of the wafer 1 are removed by using the SC-1 solution (APM solution) including a mixed solution of ammonium hydroxide (NH₄OH), hydrogen peroxide (H₂O₂) and water (H₂O). The temperature for the wafer 1 is set to about 80° C. and the treating time is set to about 10 to 20 min.

[0122] Then, after rinsing the wafer 1 with pure water, the surface of the wafer 1 is cleaned by using the cleaning solution according to this invention. Also in this case, it is not necessary to elevate the temperature of the cleaning solution according to this invention upon use and it can be used within a temperature range about from 15° C. to 45° C. An appropriate temperature range is usually about from 16° C. to 35° C. and, preferably, about from 18° C. to 28° C. Further, the treating time within the temperature range is about 5 min at the longest and, usually, a range from 50 sec to 2 min may suffice.

[0123] Then, after rinsing the wafer 1 with pure water and then removing the water content on the surface by the drying described above, the wafer 1 is transported to the succeeding step. Subsequent steps are identical with those in Embodiment 1.

[0124] Since the cleaning solution in this embodiment contains highly electron attractive F (fluorine), metals are easily dissolved in the cleaning solution and hydrofluoric acid added in a slight amount slightly etches the surface of the gate insulating film 6 and the surface of the substrate 1, it has a feature capable of removing metals taken into the surface of the gate insulating film 6 and the surface of the substrate 1 at a low temperature in a short period of time. Further, since the hydrofluoric acid concentration is low, the gate insulation film 6 or the substrate 1 is not etched unnecessarily.

[0125] Further, since the cleaning solution in this embodiment contains hydrogen peroxide tending to easily ionize W constituting the portion of the gate electrode 7, scraping of the W film can be minimized because the treatment can be applied at low temperature in a short period of time, while cleaning at high temperature for long time would scrape or eliminate a portion of the gate electrode 7 (W film).

[0126]FIG. 17 shows a relation between the cleaning time and the metal contamination removal efficiency as a result of experiment using the cleaning solution according to this invention. Experiment was conducted at a treating temperature of 23° C. It can be seen from the result that the cleaning solution according to this invention can effectively remove metal contamination at a low temperature and in a short period of time.

[0127]FIG. 18 shows a result of an experiment measuring the effect of the hydrochloric acid to hydrofluoric acid ratio on the etching rate of the silicon oxide film. It can be seen from the result that etching rate of the silicon oxide film is lowered as the hydrochloric acid to hydrofluoric acid ratio is lowered. Accordingly, it is preferred to use the cleaning solution while lowering the hydrochloric acid to hydrofluoric acid ratio in the cleaning step, for example, the cleaning step after forming the gate electrode 7, where removal of metal contamination is required while suppressing etching of the silicon oxide film (gate insulation film) as less as possible. A practical range of use is hydrochloric acid:hydrofluoric acid=about 5 to 1500:1 (weight ratio) and, preferably, hydrochloric acid:hydrofluoric acid=5 to 1000:1 (weight ratio) and, more preferably, hydrochloric acid:hydrofluoric acid=10 to 30:1 (weight ratio).

[0128] As described above, by using the cleaning solution according to this embodiment, metal contamination can be removed reliably while suppressing the etching (scraping) of the gate insulation film 6 or the substrate 1 to the utmost.

[0129] Further, since it is possible to surely remove metal contamination while suppressing etching (scraping) of the W film constituting the gate electrode 7 to the utmost, a fabrication margin for the gate electrode 7 can be decreased to effectively enhance the refinement of devices.

[0130] Further, when the cleaning solution according to this invention capable of effectively removing metal contamination at a low temperature in a short period of time is used, it is possible to reduce the operation cost of the cleaning apparatus, improve the throughput of the cleaning step and forward the wafer-by-wafer treatment.

[0131] The invention made by the present inventor has been described concretely with reference to the embodiments as described above, but the invention is not limited only to the preferred embodiments and it will be apparent that various modification are possible within a scope not departing the purpose thereof.

[0132] In the preferred embodiment described above, the cleaning treatment before forming the gate insulation film and the cleaning treatment after forming the gate electrode have been explained but the cleaning solution according to this invention is applicable generally to cleaning steps for removing metal contamination. Further, this invention is applicable not only to the cleaning for the wafer surface but also to the cleaning for the wafer back face.

[0133] As has been explained above, descriptions have been made to a case of applying the invention made by the present inventors mainly to a fabrication method for a semiconductor device having CMOS circuits as the application use constituting the background thereof but the invention is not restricted only thereto and various applications are possible. For example, it is applicable also to a fabrication method for a semiconductor device having memory circuits such as DRAM (Dynamic Random Access Memory), SRAM (Static Random Access memory) or flash memory (EEPROM: Electric Erasable Programmable Read Only Memory), a fabrication method for a semiconductor device having logic circuits such as microprocessors and a fabrication method of mixed mount type where the memory circuit and a logic circuit disposed on one identical semiconductor substrate. Further, it is applicable also to a fabrication method for liquid crystal substrates.

[0134] The effect obtained by representatives among the inventions disclosed in the present application are to be explained briefly as below.

[0135] Metal contamination can be removed at a low temperature in a short period of time by using an aqueous solution containing 0.1 to 15% by weight of hydrochloric acid, 0.01 to 0.3% by weight of hydrofluoric acid and 0.1 to 15% by weight of hydrogen peroxide as a cleaning solution upon cleaning a semiconductor substrate. 

What is claimed is:
 1. A fabrication method for a semiconductor device comprising the step of cleaning a main surface of a semiconductor wafer by using an aqueous solution containing 0.1 to 15% by weight of hydrochloric acid, 0.01 to 0.3% by weight of hydrofluoric acid and 0.1 to 15% by weight of hydrogen peroxide.
 2. A fabrication method for a semiconductor device according to claim 1 , wherein the aqueous solution contains 0.3 to 5% by weight of hydrochloric acid, 0.02 to 0.2% by weight of hydrofluoric acid and 0.3 to 5% by weight of hydrogen peroxide.
 3. A fabrication method for a semiconductor device according to claim 2 , wherein the aqueous solution contains 0.5 to 3% by weight of hydrochloric acid, 0.03 to 0.1% by weight of hydrofluoric acid and 0.5 to 3% by weight of hydrogen peroxide.
 4. A fabrication method for a semiconductor device according to claim 1 , wherein the ratio of hydrochloric acid to hydrofluoric acid contained in the aqueous solution is: hydrochloric acid:hydrofluoric acid=5 to 1500:1 (by weight ratio).
 5. A fabrication method for a semiconductor device according to claim 4 , wherein the ratio of hydrochloric acid to hydrofluoric acid contained in the aqueous solution is: hydrochloric acid:hydrofluoric acid=5 to 1000:1 (by weight ratio).
 6. A fabrication method for a semiconductor device according to claim 5 , wherein the ratio of hydrochloric acid to hydrofluoric acid contained in the aqueous solution is: hydrochloric acid:hydrofluoric acid=10 to 30:1 (by weight ratio).
 7. A fabrication method for a semiconductor device according to claim 1 , wherein the cleaning temperature for the semiconductor wafer is from 15 to 40° C.
 8. A fabrication method for a semiconductor device according to claim 7 , wherein the cleaning temperature for the semiconductor wafer is from 16 to 35° C.
 9. A fabrication method for a semiconductor device according to claim 8 , wherein the cleaning temperature for the semiconductor wafer is from 18 to 28° C.
 10. A fabrication method for a semiconductor device according to claim 1 , wherein the semiconductor wafers are cleaned by a wafer-by-wafer system.
 11. A fabrication method for a semiconductor device comprising the steps of: (a) depositing a conductive film containing a metal over the main surface of a semiconductor wafer, (b) patterning the conductive film and, (c) cleaning the main surface of the semiconductor wafer by using an aqueous solution containing 0.1 to 15% by weight of hydrochloric acid, 0.01 to 0.3% by weight of hydrofluoric acid and 0.1 to 15% by weight of hydrogen peroxide after the step (b).
 12. A fabrication method for a semiconductor device according to claim 11 , wherein the metal contains W or Mo.
 13. A fabrication method for a semiconductor device according to claim 11 , wherein the step of patterning the conductive film is a step of forming the gate electrode of an MISFET.
 14. A fabrication method for a semiconductor device according to claim 13 , which further comprises, after the step (c), (d) cleaning the main surface of the semiconductor wafer with pure water, and (e) drying the main surface of the semiconductor wafer after the step (d).
 15. A fabrication method for a semiconductor device according to claim 14 , which further comprises, after the step (e), the steps of: (f) forming source and drain of an MISFET to the semiconductor wafer on both sides of the gate electrode, (g) forming, after the step (f), an insulation film over the gate electrode, (h) forming a contact hole for exposing the surface of the source and drain by etching the insulation film, (i) cleaning the inside of the contact hole by using the aqueous solution of the same composition as that for the aqueous solution described above and (j) forming, after the step (i), metal wirings electrically connected with the source and drain through the contact hole in the insulation film.
 16. A fabrication method for a semiconductor device according to claim 11 , wherein the aqueous solution contains 0.3 to 5% by weight of hydrochloric acid, 0.02 to 0.2% by weight of hydrofluoric acid and 0.3 to 5% by weight of hydrogen peroxide.
 17. A fabrication method for a semiconductor device according to claim 16 , wherein the aqueous solution contains 0.5 to 3% by weight of hydrochloric acid, 0.03 to 0.1% by weight of hydrofluoric acid and 0.5 to 3% by weight of hydrogen peroxide.
 18. A fabrication method for a semiconductor device according to claim 11 , wherein the ratio of hydrochloric acid to hydrofluoric acid contained in the aqueous solution is hydrochloric acid:hydrofluoric acid=5 to 1500:1 (by weight ratio).
 19. A fabrication method for a semiconductor device according to claim 18 , wherein the ratio of hydrochloric acid to hydrofluoric acid contained in the aqueous solution is hydrochloric acid:hydrofluoric acid=5 to 1000:1 (by weight ratio).
 20. A fabrication method for a semiconductor device according to claim 19 , wherein the ratio of hydrochloric acid to hydrofluoric acid contained in the aqueous solution is hydrochloric acid:hydrofluoric acid=10 to 30:1 (by weight ratio).
 21. A fabrication method for a semiconductor device according to claim 11 , wherein the cleaning temperature for the semiconductor wafer is from 15 to 40° C.
 22. A fabrication method for a semiconductor device according to claim 21 , wherein the cleaning temperature for the semiconductor wafer is from 16 to 35° C.
 23. A fabrication method for a semiconductor device according to claim 22 , wherein the cleaning temperature for the semiconductor wafer is from 18 to 28° C.
 24. A fabrication method for a semiconductor device according to claim 11 , wherein the cleaning time for the semiconductor wafer is 5 min or less.
 25. A fabrication method for a semiconductor device according to claim 24 , wherein the cleaning time for the semiconductor wafer is 2 min or less.
 26. A fabrication method for a semiconductor device according to claim 25 , wherein the cleaning time for the semiconductor wafer is 50 sec or less.
 27. A fabrication method for a semiconductor device according to claim 11 , wherein the semiconductor wafers are cleaned by a wafer-by-wafer method.
 28. A fabrication method for a semiconductor device comprising the steps of: (a) cleaning the main surface of the semiconductor wafer by using an aqueous solution containing 0.1 to 15% by weight of hydrochloric acid, 0.01 to 0.3% by weight of hydrofluoric acid and 0.1 to 15% by weight of hydrogen peroxide and (b) forming, after the step (a), a gate insulation film of an MISFET over the main surface of the semiconductor wafer.
 29. A fabrication method for a semiconductor device according to claim 28 , wherein the aqueous solution contains 0.3 to 5% by weight of hydrochloric acid, 0.02 to 0.2% by weight of hydrofluoric acid and 0.3 to 5% by weight of hydrogen peroxide.
 30. A fabrication method for a semiconductor device according to claim 29 , wherein the aqueous solution contains 0.5 to 3% by weight of hydrochloric acid, 0.03 to 0.1% by weight of hydrofluoric acid and 0.5 to 3% by weight of hydrogen peroxide.
 31. A fabrication method for a semiconductor device according to claim 28 , wherein the ratio of hydrochloric acid to hydrofluoric acid contained in the aqueous solution is hydrochloric acid:hydrofluoric acid=5-1500:1 (by weight ratio).
 32. A fabrication method for a semiconductor device according to claim 31 , wherein the ratio of hydrochloric acid to hydrofluoric acid contained in the aqueous solution is hydrochloric acid:hydrofluoric acid=5-1000:1 (by weight ratio).
 33. A fabrication method for a semiconductor device according to claim 32 , wherein the ratio of hydrochloric acid to hydrofluoric acid contained in the aqueous solution is hydrochloric acid:hydrofluoric acid=10-30:1 (by weight ratio).
 34. A fabrication method for a semiconductor device according to claim 28 , wherein the cleaning temperature for the semiconductor wafer is from 15 to 40° C.
 35. A fabrication method for a semiconductor device according to claim 34 , wherein the cleaning temperature for the semiconductor wafer is from 16 to 35° C.
 36. A fabrication method for a semiconductor device according to claim 35 , wherein the cleaning temperature for the semiconductor wafer is from 18 to 28° C.
 37. A fabrication method for a semiconductor device according to claim 28 , wherein the semiconductor wafers are cleaned by a wafer-by-wafer method.
 38. A fabrication method for a semiconductor device comprising the steps of: (a) forming a first film pattern containing a refractory metal base film over a silicon base surface on the main surface of the wafer, (b) acting a first alkaline cleaning solution on a first main surface of the wafer formed with the first film pattern. (c) acting a second acidic cleaning solution containing hydrofluoric acid, hydrochloric acid, hydrogen peroxide and water over the first main surface of the wafer formed with the first film pattern and, (d) applying, after completion of both of the step (b) and the (c), a high temperature heat treatment at a temperature higher than 600° C. to the wafer without cleaning with a third cleaning solution containing hydrofluoric acid of a different composition from that of the second cleaning solution to the wafer.
 39. A fabrication method for a semiconductor device according to claim 38 , wherein the refractory metal base film is a film including tungsten or molybdenum as a main constituent.
 40. A fabrication method for a semiconductor device according to claim 39 , wherein the first cleaning solution contains ammonium hydroxide, hydrogen peroxide and water. 